Liquid Phase Oxidation via Heterogeneous Catalysis
Organic Synthesis and Industrial Applications

Sets the stage for environmentally friendly industrial organic syntheses

From basic principles to new and emerging industrial applications, this book offers comprehensive coverage of heterogeneous liquid-phase selective oxidation catalysis. It fully examines the synthesis, characterization, and application of catalytic materials for environmentally friendly organic syntheses. Readers will find coverage of all the important classes of catalysts, with an emphasis on their stability and reusability.

Liquid Phase Oxidation via Heterogeneous Catalysis features contributions from an international team of leading chemists representing both industry and academia. The book begins with a chapter on environmentally benign oxidants and then covers:

• Selective oxidations catalyzed by TS-1 and other metal-substituted zeolites
• Selective catalytic oxidation over ordered nanoporous metallo-aluminophosphates
• Selective oxidations catalyzed by mesoporous metal-silicates
• Liquid phase oxidation of organic compounds by supported metal-based catalysts
• Selective liquid phase oxidations in the presence of supported polyoxometalates
• Selective oxidations catalyzed by supported metal complexes
• Liquid phase oxidation of organic compounds by metal-organic frameworks
• Heterogeneous photocatalysis for selective oxidations with molecular oxygen

All the chapters dedicated to specific types of catalysts follow a similar organization and structure, making it easy to compare the advantages and disadvantages of different catalysts. The final chapter examines the latest industrial applications, such as the production of catechol and hydroquinone, cyclohexanone oxime, and propylene oxide.

With its unique focus on liquid phase heterogeneous oxidation catalysis, this book enables researchers in organic synthesis and oxidation catalysis to explore and develop promising new catalytic materials and synthetic routes for a broad range of industrial applications.

Preface xi

Contributors xiii

Abbreviations xv

1 Environmentally Benign Oxidants 1
Giorgio Strukul and Alessandro Scarso

1.1 Introduction 1

1.2 Oxygen (Air) 3

1.3 Alkylhydroperoxides 5

1.4 Hydrogen Peroxide 9

1.5 Conclusions 16

References 17

2 Oxidation Reactions Catalyzed by Transition-Metal-Substituted Zeolites 21
Mario G. Clerici and Marcelo E. Domine

2.1 Introduction 21

2.2 Synthesis and Characterization of Zeolites 22

2.2.1 Isomorphous Metal Substitution 23

2.2.2 Synthesis of Titanium Silicalite-1 (TS-1) 24

2.2.3 Characterization of Titanium Silicalite-1 (TS-1) 26

2.2.4 Ti-Beta, Synthesis and Characterization 30

2.2.5 Other Ti Zeolites 32

2.2.6 Other Metal Zeolites 33

2.3 Catalytic Properties 34

2.3.1 Hydroxylation of Alkanes 34

2.3.2 Hydroxylation of Aromatic Compounds 40

2.3.3 Oxidation of Olefinic Compounds 47

2.3.4 Oxidation of Alcohol and Ether Compounds 59

2.3.5 Reactions of Carbonyl Compounds 60

2.3.6 Oxidation of N-Compounds 63

2.3.7 Oxidation of S-Compounds 65

2.4 Mechanistic Aspects 66

2.4.1 The Nature of Active Species 66

2.4.2 Hydroxylation 69

2.4.3 Epoxidation 71

2.4.4 Oxidation of Alcohols 72

2.4.5 Ammoximation 73

2.4.6 Decomposition of Hydrogen Peroxide 74

2.4.7 Active Species, Adsorption and Catalytic Activity 74

2.5 Stability of Metal-Substituted Zeolites to Reaction Conditions 77

2.6 Conclusions 78

References 80

3 Selective Catalytic Oxidation over Ordered Nanoporous Metallo-Aluminophosphates 95
Parasuraman Selvam and Ayyamperumal Sakthivel

3.1 Introduction 95

3.2 Synthesis 100

3.2.1 Microporous Aluminophosphates 100

3.2.2 Mesoporous Aluminophosphates 102

3.3 Characterization 103

3.4 Catalytic Properties 106

3.4.1 Oxidation of Hydrocarbons 106

3.4.2 Oxidation of Olefins 110

3.4.3 Oxidation of Alcohols 111

3.4.4 Oxidation of Phenols 113

3.4.5 Ammoximation and Ammoxidation 114

3.4.6 Baeyer–Villiger Oxidation 116

3.4.7 Oxidation of Heterocycles 116

3.5 Mechanistic Aspects 116

3.6 Catalysts Stability 118

3.7 Conclusion 119

References 120

4 Selective Oxidations Catalyzed by Mesoporous Metal Silicates 127
Oxana A. Kholdeeva

4.1 Introduction 127

4.2 Synthesis and Characterization 128

4.2.1 General Synthetic Approaches 128

4.2.2 Characterization Techniques 129

4.2.3 Sol-Gel Synthesis of Amorphous Mixed Oxides 132

4.2.4 Thermolytic Molecular Precursor Method 136

4.2.5 Templated Synthesis of Ordered Metal Silicates 136

4.2.6 Postsynthesis Modifications 156

4.2.7 Organic–Inorganic Hybrid Materials 162

4.3 Catalytic Properties 163

4.3.1 Oxidation of Alkanes 163

4.3.2 Oxidation of Aromatic Compounds 167

4.3.3 Oxidation of Olefins 172

4.3.4 Oxidation of Alcohols 182

4.3.5 Oxidation of Ketones and Aldehydes 183

4.3.6 Oxidation of S-compounds 185

4.3.7 Oxidation of Amines 188

4.4 Mechanistic Aspects 189

4.5 Stability 194

4.5.1 Mechanisms of Deactivation 194

4.5.2 Solving Problem of Hydrothermal Stability 197

4.5.3 Hydrothermally Stable Catalysts: Scope and Limitations 199

4.6 Conclusions and Outlook 200

References 201

5 Liquid Phase Oxidation of Organic Compounds by Supported Metal-Based Catalysts with a Focus on Gold 221
Cristina Della Pina, Ermelinda Falletta, and Michele Rossi

5.1 Introduction 221

5.2 Catalyst Preparation and Characterization 222

5.3 Catalytic Properties 224

5.3.1 Oxidation of Hydrocarbons 224

5.3.2 Oxidation of Alcohols and Phenols 228

5.3.3 Oxidation of Carbohydrates: The Case of Glucose 241

5.3.4 Oxidation of Amines and Aminoalcohols 244

5.3.5 Oxidative Polymerization of Aniline and Pyrrole 245

5.4 Reaction Mechanisms 250

5.5 Catalyst Stability 254

5.6 Conclusions 256

References 256

6 Selective Liquid Phase Oxidations in the Presence of Supported Polyoxometalates 263
Craig L. Hill and Oxana A. Kholdeeva

6.1 Introduction 263

6.2 Synthesis and Characterization 266

6.2.1 Choice of POM 266

6.2.2 Embedding POM into Silica and Other Matrixes 267

6.2.3 Adsorption on Active Carbon 271

6.2.4 Electrostatic Attachment 273

6.2.5 Dative and Covalent Binding 283

6.3 Catalytic Properties 287

6.3.1 Oxidation of Alkanes 287

6.3.2 Oxidation of Aromatic Compounds 288

6.3.3 Oxidation of Olefins 288

6.3.4 Oxidation of Alcohols 297

6.3.5 Oxidation of Aldehydes 298

6.3.6 Co-Oxidation of Alkenes and Aldehydes 299

6.3.7 Oxidation of S-containing Compounds 301

6.4 Mechanistic Aspects 304

6.5 Stability 307

6.6 Conclusions 309

References 311

7 Selective Oxidations Catalyzed by Supported Metal Complexes 321
Alexander B. Sorokin

7.1 Introduction 321

7.2 Synthesis and Characterization 323

7.2.1 General Synthetic Strategies 324

7.2.2 Metal Porphyrins 329

7.2.3 Metal Phthalocyanines 331

7.2.4 Complexes with Other Macrocyclic Ligands 336

7.2.5 Chiral Complexes 337

7.3 Catalytic Properties and Stability 338

7.3.1 Oxidation of Alkanes 339

7.3.2 Oxidation of Olefins 344

7.3.3 Oxidation of Aromatic Hydrocarbons 352

7.3.4 Oxidation of Substituted Phenols 353

7.3.5 Oxidation of Alcohols 356

7.3.6 Miscellaneous Oxidations 359

7.4 General Remarks on Stability 362

7.5 Conclusion and Perspectives 364

References 365

8 Liquid Phase Oxidation of Organic Compounds by Metal-Organic Frameworks 371
Young Kyu Hwang, Gerard Ferey, U-Hwang Lee, and Jong-San Chang

8.1 Introduction 371

8.2 Characteristics and Structures 372

8.2.1 Characteristics 372

8.2.2 Structures 374

8.2.3 Syntheses 378

8.2.4 Active Sites 380

8.3 Catalytic Properties 388

8.3.1 Oxidation of Cycloalkanes 388

8.3.2 Oxidation of Aromatic Compounds 389

8.3.3 Oxidation of Olefins 393

8.3.4 Oxidation of Alcohols and Phenols 398

8.3.5 Oxidation of Sulfides 399

8.4 Mechanistic Aspects 400

8.5 Stability 402

8.5.1 Thermal and Chemical Stability 402

8.5.2 Leaching of Active Metal Components 404

8.6 Conclusion 405

References 405

9 Heterogeneous Photocatalysis for Selective Oxidations with Molecular Oxygen 411
Andrea Maldotti, Rossano Amadelli, and Alessandra Molinari

9.1 Introduction 411

9.2 Catalysts Preparation and Mechanistic Aspects 413

9.2.1 Titanium Dioxide 413

9.2.2 Highly Dispersed Oxides 416

9.2.3 Polyoxotungstates 418

9.3 Catalytic Properties 422

9.3.1 Oxidation of Alkanes 422

9.3.2 Oxidation of Aromatic Compounds 427

9.3.3 Oxidation of Alcohols 430

9.3.4 Oxidation of Olefins 436

9.4 Stability 438

9.5 Conclusions 443

References 444

10 Industrial Applications 451

10.1 The Hydroxylation of Phenol to Hydroquinone and Catechol 451
Ugo Romano and Marco Ricci

10.1.1 The Discovery of TS-1 451

10.1.2 The Hydroxylation of Phenol 452

10.1.3 The Industrial Process 456

10.1.4 Other Processes Exploiting TS-1 460

References 461

10.2 The Greening of Nylon: The Ammoximation Process 462
Franco Rivetti and Roberto Buzzoni

10.2.1 Nylon-6 and e-Caprolactam, Outlook and Industrial Production 462

10.2.2 TS-1 Catalyzed Ammoximation 466

10.2.3 Eni Cyclohexanone Ammoximation Process 467

10.2.4 Salt-Free Caprolactam Production 470

10.2.5 Other TS-1-Catalyzed Ammoximation Reactions and Related Processes of Industrial Relevance 470

10.2.6 Conclusion 471

References 472

10.3 Production of Propylene Oxide 474
Anna Forlin, Massimo Bergamo, and Joerg Lindner

10.3.1 Propylene Oxide Production via Ethylbenzene Hydroperoxide Route 476

10.3.2 Propylene Oxide Production via Cumene Hydroperoxide Route 480

10.3.3 Propylene Oxide Production via Hydrogen Peroxide Route 483

10.3.4 Conclusions 487

References 494

10.4 Engineering Aspects of Liquid Phase Oxidations 496
Bruce D. Hook

10.4.1 Heterogeneous Liquid Phase Systems 496

10.4.2 Temperature-Control Requirements 499

10.4.3 Packed-Bed Reactors 500

10.4.4 Three-Phase Systems – Gas, Liquid, Solid 501

10.4.5 Oxidant Selection 503

10.4.6 Summary 505

References 506

Index 507

MARIO G. CLERICI, Laurea in Chemistry, has over thirty-five years of industry experience working with organic synthesis and homogeneous and heterogeneous catalysis in the ENI group. He also taught courses in the Department of Industrial Chemistry at the University of Turin, Italy, for eight years and served as a scientific expert on clean catalytic technologies at the International Centre for Science and High Technology, Trieste. A recipient of the Donald W. Breck Award, Dr. Clerici holds more than forty patents.

OXANA A. KHOLDEEVA, PhD, is Head of the Research Group for Heterogeneous Catalysis for Liquid-Phase Selective Oxidations at the Boreskov Institute of Catalysis, Russia, and a visiting professor at several universities in Europe and the United States. As the author of over 100 articles and nine patents, she participated in the expert panel of the sixth World Congress on Oxidation Catalysis and is a member of the International Advisory Board for the International Symposium on Activation of Dioxygen and Homogeneous Catalytic Oxidation (ADHOC).